Halogen-containing compound and method of preparing same



Patented 3, 1934 1 BALOGKN-OONTAINING COMPOUND AND mop or rasraamc SAME Donald Drake comm, Wilmington, Del., as-

signer to E. I. in Pont dc Nemours & Company, Wilmington, Del, a corporation of Delaware No Drawing. Application January 26, 1932, Sula! No. 589,051

13 Claims. (01. 260-162) NT OFFICE This invention pertains to new and useful products and process for preparing same. More particularly theinvention relates to the chlorination of dichloro-2A-butene-2 and tonovel chlorina- 5 tion products produced thereby.

A copending application of Carothers and Collins, Serial No. 409,538, filed October 22, 1930 discloses the preparation of certain new compounds by the addition of hydrogen chloride to monoi vinylacetylene. Included among these compounds is 'dichloro-zA-butene-a, 'CHs-C(Cl)= CH-CH-.-Cl. The present invention deals with the chlorination of this compound and it embraces the novel products which are produced by l the said chlorination.

It is an object of this invention to halogenate dihalogen-2,4-butene-2 with the production of new compounds. It is a more specific object to subject dichloro-2,4-butene-2 to chlorination un-- der variable'conditions to produce novel and valuable chloro derivatives in desired quantities.

According to the present inventiondichloro- 2,4-butene-2 either dissolved in an inert solvent such as carbon tetrachloride or not, is treated with chlorine at temperatures varying from considerably below normal room temperatures up to the boiling point of the compound. This is suitably done by passing gaseous chlorine into the compound, the conditions under which chlorination takes place being controlled according to' the product which it is most desired toproduce, the proportion of the various products difiering considerably according tothe particular conditions chosen. The chlorination in this manner of dichloro- 2,4 -butene-2 leads to the formation of the following novel products:

' The various products "are readily separated from one another by fractional The following examples illustrate this process:

Eamon: 1

Chlorination of dichloro-ZA-but'enc-Z at 0-8 C.

- Into 250 g. (2 mole) of 2.-2 dissolvedin500 cc. of

produced a substantial amount of pentachloroerably larger yield of the trichlorobute'ne:

was passed dry chlorine, the temperature being maintained at 0-8 C. After 120 g. of chlorine had been absorbed, the chlorination was stopped. In the process of chlorinationa large amount of hydrogen chloride was evolved. The crude prod- 6; uct in carbon tetrachloride was washed, dried, and fractionated in a precision still. Two fractions were thus obtained: One was trichloro-2,3,4-butene-l (37 g. or 14% yield) which boiled at 67 C. under 39 mm. pressure and had the refrac- 65 tivity ug 1.4944 and the density I v to I n gi 1,3430;-

the other fraction was tetrachloro-2,2,3,4-butane (68 g. or 21% yield) which boiled at C. under 7 32 mm. pressure and had the refractivity Q in 2, 1.4204. I Simultaneously with the formation of the trichlorobutene and the tetrachlorobutene there is 85 1,2,2,3,4-butane boiling at 85 C./ 10 mm.

The following example illustrates the use of I very low temperatures for producing a consid- EXAMPLE 2 I Chlofination of dichloro-2,4-butene-2 at -50 0..

Six moles .(750 g.) of dich1oro-2,4-butene-2, with or with at a solvent such as carbon tetrachloride, are reated with chlorine at a temperature of about -50 C. with constant mechanical stirring, until an increase in weight amounting to about 300 g. is attained. This operation is attended by a copious evolution of HCl gas. The mixture is then allowed to warm up while a stream of air is passed through it to drive oil -the dissolved HCl. The mixture is then dried over a drying agent such as MgSO4 and an alkaline agent such as K200: and distilled.

The following example indicates an approach to the upper range of operative temperatures, and clearly illustrates the great diflerence in yields of the various products under difl'erent' conditions and temperatures; a

Exams: 3

Chlorination o! dichloro-2,4-butene-2 at 5 Two moles (250 g.) of dichloro-2,4-butene-2 are treated with chlorine at a temperature of 45-80 C. with constant mechanical stirring,

' agent such as K200: and distilled. As in the preceding example, substantially three fractionsare collected:

1. Trichioro-2,3,4-butene-1 at 37-41 C./10 mm.

2. Tetrachloro-2,2,3,4-butane at 52-60 0/!) "mm.

3. Pentachloro-1,2,2,3, 4-butaneat78-84C/9 mm.

From the above examples it will be noted that the yields of trichlorobutene are considerably improved by operating at lower temperatures, the yields of the tetrachloro and pentachloro compounds being varied accordingly in the manner indicated in the examples. Thus, the temperature conditions may be regulated according to the character of the chloro compound which it is desired to produce. At low temperatures large amounts ofhydrogen chloride are evolved during the reaction; at higher temperatures very. little hydrogen chloride is evolved and at those temperatures the tetrachloro compound is 'produced chiefly.

If the reaction is'conducted in precisely the same way but at a temperature of 45-60 C. very little hydrogen chloride is evolved and the principal product consists of tetrachlorobutane as already described above.

The preferred temperature range for the reaction may' vary from C. up to the point of dichloro-2,4-butene-2.

Catalysts may be used to accelerate the chlorination reaction if desired. Typical catalysts are antimony pentachloride, cuprous chloride, cupric chloride, stannic chloride, ferric chloride, aluminum chloride, etc. The use of catalysts, however, frequently leads to the formation of byproducts and makes the process of purification more diiiicult.

While no solvent is necessary, the optional use of carbon tetrachloride as a solvent has beenmentioned. Other solvents having similar properties may, however, be substituted for carbon tetrachloride, e. g., toluene, carbon bisulfide, and chloroform.

The novel compounds described herein have a high degree of utility. For example, in a copending applicaton of Carothers and Berchet. Serial No. 589,052, filed January 26, 1932, there is described a method for treating trichloro-2,3,4- butene-l with caustic to split off hydrogen chloride, the resulting chloro substituted butadiene being easily susceptible to polymerization to produce valuable; compositions. A

It will be understood that other halogen-2,4- butene-2 may be halogenated in a manner simiv lar to that described for the chlorination of dichloro-2,4-butene-2 with production of related novel products.

The above description and examples are illustrative only and should not be construed as limiting the scope of the invention. Any modification or variation therefrom which conforms to the spirit of the invention is intended to be included within the scope of the claims.

I claim:

1. The process which comprises halogenating a .dihalogen-2,4-butene-2.

. 2. The process which comprises halogenating .a dihalogen-2,4-butene-2 in the presence of a .dichloro-2,4-butene-2 in the presence of a solvent. 5

7. The process which comprises chlorinating dichloro-2,4-butene-2 at a temperature of from 80 C. to the boiling point of dichloro-2,4-butene-2.

8. The process which comprises chlorinating dichloro-2,4-butene-2 at. a temperature approximately 50 C.

9. The process which comprises chlorinating dichloro-2,4-butene-2 in the presence of a chicrination catalyst.

10. As a new chemical compound, trihalogen- 2,3,4-butene-1.

11. As a new chemical compound, tetrahalogen-2,2,3,4-butane.

12. As a new chemical compound, trichloro- 2,3,4-butene-1.

13. As a new chemical compound, tetrachloro- 2,2,3,4-butane.

a DONALD D. COFFMAN. 

